阅读说明：本技术 一种石墨烯抗静电医用鞋底复合材料及其制备方法 (Graphene antistatic medical sole composite material and preparation method thereof ) 是由 丁天宁 丁德材 丁幼丝 于 2020-12-11 设计创作，主要内容包括：本发明提供一种石墨烯抗静电医用鞋底复合材料及其制备方法,包括以下原料：丁基橡胶,天然橡胶,顺丁橡胶,三元乙丙胶,白炭黑,石墨烯,抗静电粉,流动助剂,氧化锌,硬脂酸锌,硬脂酸,无味交联剂,发泡剂。所述复合材料制备方法如下：将用流动助剂和硬脂酸处理的石墨烯加热后,依次加入丁基橡胶、天然橡胶、顺丁橡胶和三元乙丙橡胶,在混炼机中进行混炼,得到混合原胶；再向混合原胶中加入白炭黑,抗静电粉,氧化锌,硬脂酸锌,无味交联剂,发泡剂进行再次混炼硫化交联,即得石墨烯抗静电医用鞋底复合材料,该复合材料具有抗静电、抗菌、弹性高、耐磨性好,无毒,不易变形,易清洁等优点,从而其作为医用鞋底使用效果更好。(The invention provides a graphene antistatic medical sole composite material and a preparation method thereof, wherein the graphene antistatic medical sole composite material comprises the following raw materials: butyl rubber, natural rubber, butadiene rubber, ethylene propylene diene monomer, white carbon black, graphene, antistatic powder, a flow aid, zinc oxide, zinc stearate, stearic acid, an odorless crosslinking agent and a foaming agent. The preparation method of the composite material comprises the following steps: heating graphene treated by a flow aid and stearic acid, sequentially adding butyl rubber, natural rubber, butadiene rubber and ethylene propylene diene monomer rubber, and mixing in a mixing roll to obtain mixed virgin rubber; and then adding the white carbon black, the antistatic powder, the zinc oxide, the zinc stearate, the tasteless cross-linking agent and the foaming agent into the mixed virgin rubber for mixing, vulcanizing and cross-linking again to obtain the graphene antistatic medical sole composite material.)

1. The graphene antistatic medical sole composite material is characterized by comprising the following raw materials in parts by weight: 25-35 parts of butyl rubber, 35-45 parts of natural rubber, 5-15 parts of butadiene rubber, 10-20 parts of ethylene propylene diene monomer, 3-8 parts of white carbon black, 0.5-10 parts of graphene, 4-8 parts of antistatic powder, 0.5-1.5 parts of a flow promoter, 5-10 parts of zinc oxide, 1-3 parts of zinc stearate, 0.4-2 parts of stearic acid, 0.5-2.5 parts of an odorless cross-linking agent and 2-5 parts of a foaming agent.

2. The graphene antistatic medical sole composite material as claimed in claim 1, is characterized in that the basic composition of the composite material comprises the following raw materials in parts by weight: 30 parts of butyl rubber, 40 parts of natural rubber, 10 parts of butadiene rubber, 15 parts of ethylene propylene diene monomer, 5 parts of white carbon black, 5 parts of graphene, 5 parts of antistatic powder, 1.0 part of flow aid, 7 parts of zinc oxide, 2 parts of zinc stearate, 1 part of stearic acid, 1.5 parts of odorless cross-linking agent and 3 parts of foaming agent.

3. The graphene antistatic medical sole composite material according to claim 1, wherein the antistatic powder is ethoxylated aliphatic alkylamine, and the flow aid is one of tetramethylthiuram disulfide and tetramethylthiuram hexasulfide.

4. The graphene natural rubber antibacterial crawling composite material for children as claimed in claim 1, wherein the odorless cross-linking agent is di-tert-butylperoxydiisopropylbenzene, and the foaming agent is one of azodicarbonamide, diphenyl sulfonyl hydrazide ether and p-toluenesulfonyl hydrazide.

5. The graphene antistatic medical sole composite material as claimed in claim 1 or 2, comprising the following steps:

step 1, heating graphene treated by a flow aid and stearic acid, sequentially adding butyl rubber, natural rubber, butadiene rubber and ethylene propylene diene monomer rubber, and mixing in a mixing roll to obtain mixed virgin rubber;

and 2, adding white carbon black, antistatic powder, zinc oxide, zinc stearate, a tasteless cross-linking agent and a foaming agent into the mixed virgin rubber, and mixing, vulcanizing and crosslinking again to obtain the graphene antistatic medical sole composite material.

6. The preparation method of the graphene antistatic medical sole composite material according to claim 5, wherein the graphene treatment in the step 1 specifically comprises the steps of mixing the flow aid, stearic acid and deionized water according to a weight ratio of 0.5-1.5: 0.4-2: 100, heating to 100-160 ℃ after uniform mixing, slowly and gradually adding the graphene, continuously stirring, and continuously stirring for 1-3 hours after adding, wherein the adding amount of the graphene is 0.5-10 mg/ml, so as to obtain the graphene treated by the flow aid and stearic acid.

7. The preparation method of the graphene antistatic medical sole composite material according to claim 5, wherein in the step 1, the mixing temperature is 120-180 ℃, and the mixing time is 3-6 hours.

8. The preparation method of the graphene antistatic medical sole composite material according to claim 5, wherein during vulcanization crosslinking in step 2, the graphene antistatic medical sole composite material is obtained by hot pressing on a flat vulcanizing machine at 120-160 ℃ and under the pressure of 8-10 MPa for 20-30 min, and then carrying out secondary vulcanization in an oven under the vulcanization conditions of 175-185 ℃, 2-4 h, 195-205 ℃, 2-3 h, 215-225 ℃ and 1-2 h.

Technical Field

The invention belongs to the technical field of rubber-based composite materials, and particularly relates to a graphene antistatic medical sole composite material and a preparation method thereof.

Background

The rubber material is one of indispensable and alternative key materials in the fields of national economy and high technology at present, and is widely applied to the fields of aerospace, military, transportation, high-speed rail, electronic information, energy power, national major infrastructure construction and the like. In recent years, with the progress of science and technology, the requirements on rubber materials are higher and higher, and the novel rubber materials not only need to have the performances of high strength, high elasticity and the like, but also need to have the characteristics of high wear resistance, high oil resistance, high and low temperature resistance, long service life and the like. The graphene is sp²The hybridized and connected carbon atoms are tightly packed into a new material with a single-layer two-dimensional honeycomb lattice structure. The graphene has excellent optical, electrical and mechanical properties, has important application prospects in the aspects of materials science, micro-nano processing, energy, biomedicine, drug delivery and the like, can greatly improve the mechanical properties of rubber by being filled in a small amount when being used as a reinforcing material of the rubber, can show good electrical and thermal properties, and can be used as a very ideal medical nano material.

Therefore, the research on the graphene and rubber composite material is developed, and the method has great significance for improving the overall level of the rubber industry in China. However, in the actual production process, the dispersion of graphene in the rubber matrix is always a bottleneck troubling the graphene rubber composite material, and due to the surface tension and self-aggregation, the bonding force between rubber and graphene is very low, and the graphene is easy to separate, so that the performance of the composite material is greatly reduced, and the expected effect cannot be achieved.

The medical composite material has the characteristics of high technical content and high added value, and has great development potential. As a medical composite material, the following conditions need to be met: the plasticizer used is not easy to exude from the material; heavy metal compounds are not suitable to be selected as heat stabilizers; other additives and auxiliaries have no side effect or have side reaction with materials, and the precipitation of the auxiliaries is prevented or reduced when the additive is used for a long time. Meanwhile, the sole used as a medical sole also needs to have an antistatic function so as to avoid the influence on the treatment activities of medical staff caused by static electricity generated in the walking process and the ground.

In order to solve the above problems, it is necessary to develop a graphene antistatic medical sole composite material.

Disclosure of Invention

Based on the prior art, the invention aims to provide the graphene antistatic medical sole composite material and the preparation method thereof, and the graphene antistatic medical sole composite material has the advantages of antistatic property, antibacterial property, high elasticity, good wear resistance, no toxicity, difficult deformation, easy cleaning and the like, so that the graphene antistatic medical sole composite material has a better using effect when being used as a medical sole.

In order to achieve the above purpose, the invention adopts the technical scheme that:

the graphene antistatic medical sole composite material comprises the following raw materials in parts by weight: 25-35 parts of butyl rubber, 35-45 parts of natural rubber, 5-15 parts of butadiene rubber, 10-20 parts of ethylene propylene diene monomer, 3-8 parts of white carbon black, 0.5-10 parts of graphene, 4-8 parts of antistatic powder, 0.5-1.5 parts of a flow promoter, 5-10 parts of zinc oxide, 1-3 parts of zinc stearate, 0.4-2 parts of stearic acid, 0.5-2.5 parts of an odorless cross-linking agent and 2-5 parts of a foaming agent.

In order to better realize the invention, further, the basic composition of the composite material comprises the following raw materials in parts by weight: 30 parts of butyl rubber, 40 parts of natural rubber, 10 parts of butadiene rubber, 15 parts of ethylene propylene diene monomer, 5 parts of white carbon black, 5 parts of graphene, 5 parts of antistatic powder, 1.0 part of flow aid, 7 parts of zinc oxide, 2 parts of zinc stearate, 1 part of stearic acid, 1.5 parts of odorless cross-linking agent and 3 parts of foaming agent.

In order to better realize the invention, further, the antistatic powder is ethoxylated aliphatic alkylamine, and the flow assistant is one of tetramethylthiuram disulfide and tetramethylthiuram hexasulfide.

In order to better realize the invention, further, the odorless cross-linking agent is di-tert-butylperoxydiisopropylbenzene, and the foaming agent is one of azodicarbonamide, diphenyl sulfonyl hydrazide ether and p-toluene sulfonyl hydrazide.

The invention also provides a preparation method of the graphene antistatic medical sole composite material, which comprises the following steps:

step 1, heating graphene treated by a flow aid and stearic acid, sequentially adding butyl rubber, natural rubber, butadiene rubber and ethylene propylene diene monomer rubber, and mixing in a mixing roll to obtain mixed virgin rubber;

and 2, adding white carbon black, antistatic powder, zinc oxide, zinc stearate, a tasteless cross-linking agent and a foaming agent into the mixed virgin rubber, and mixing, vulcanizing and crosslinking again to obtain the graphene antistatic medical sole composite material.

In order to better realize the method, the graphene treatment in the step 1 comprises the specific steps of mixing the flow aid, stearic acid and deionized water according to the weight ratio of 0.5-1.5: 0.4-2: 100, uniformly mixing, heating to 100-160 ℃, slowly and gradually adding the graphene, continuously stirring for 1-3 hours after adding, wherein the adding amount of the graphene is 0.5-10 mg/ml, and obtaining the graphene treated by the flow aid and stearic acid.

In order to better realize the invention, the mixing temperature in the step 1 is 120-180 ℃, and the mixing time is 3-6 h.

In order to better realize the invention, further, during vulcanization crosslinking in the step 2, hot pressing is firstly carried out on a plate vulcanizing machine for 20-30 min at 120-160 ℃ and under the pressure of 8-10 Mpa, and then secondary vulcanization is carried out in an oven under the vulcanization conditions of 175-185 ℃, 2-4 h, 195-205 ℃, 2-3 h, 215-225 ℃ and 1-2 h, so as to obtain the graphene antistatic medical sole composite material.

Advantageous effects

The invention has the following beneficial effects:

(1) the composite material contains graphene, which is used as a reinforcing material of rubber, can greatly improve the mechanical property of the rubber by filling a small amount of graphene, can show good electrical and thermal properties of the graphene, and is an ideal rubber nano material.

(2) The composite material has an antistatic effect, and the antistatic powder used in the invention is an internal mixing type antistatic agent, which is a type of antistatic agent added into rubber in the processing process of products. The antistatic agent molecule can endow the surface of a high polymer material with certain lubricity, reduce the friction coefficient, inhibit and reduce static charge generation, and has the characteristic of permanent antistatic.

(3) The cross-linking agent selected by the composite material is di-tert-butylperoxydiisopropylbenzene, no pungent odor is generated in the operation process and the prepared product, the rubber material is added during mixing, and under the condition of the same cross-linking effect, the addition amount is only 2/3 of DCP, so that the dosage is reduced, and the composite material is more environment-friendly; the foaming agent is one of azodicarbonamide, diphenyl sulfonyl hydrazide ether and p-toluene sulfonyl hydrazide, has stable property during storage, is non-toxic and non-combustible, has better compatibility with rubber during mixing, is decomposed to generate nitrogen gas to form closed holes or connected holes, has small shrinkage rate, is not easy to deform, and ensures that the holes are not easy to collapse; the auxiliary agent is not easy to exude in a finished product after being used, does not generate side reaction with other materials, is nontoxic and harmless after being used for a long time, and has no pollution and influence on hospital environment.

Detailed Description

The present invention will be described in further detail with reference to specific examples.

Example 1

The embodiment provides a graphene antistatic medical sole composite material, which comprises the following raw materials in parts by weight: 25 parts of butyl rubber, 35 parts of natural rubber, 5 parts of butadiene rubber, 10 parts of ethylene propylene diene monomer, 3 parts of white carbon black, 1 part of graphene, 4 parts of antistatic powder, 0.5 part of flow aid, 5 parts of zinc oxide, 1 part of zinc stearate, 0.4 part of stearic acid, 0.5 part of tasteless cross-linking agent and 2 parts of foaming agent.

The embodiment also provides a preparation method of the graphene antistatic medical sole composite material, which comprises the following steps:

step 1, mixing a flow aid, stearic acid and deionized water according to a weight ratio of 0.5:0.4:100, heating to 110 ℃ after uniformly mixing, slowly and gradually adding graphene, stirring continuously, stirring for 3 hours after adding, wherein the adding amount of the graphene is 1mg/ml, obtaining the flow aid and the stearic acid-treated graphene, then sequentially adding butyl rubber, natural rubber, butadiene rubber and ethylene propylene diene monomer into the flow aid and the stearic acid-treated graphene, and mixing in a mixing mill at the mixing temperature of 120 ℃ for 6 hours to obtain mixed virgin rubber;

and 2, adding white carbon black, antistatic powder, zinc oxide, zinc stearate, an odorless cross-linking agent and a foaming agent into the mixed virgin rubber, carrying out hot pressing on the mixed virgin rubber for 30min at 120 ℃ and 8Mpa in a flat vulcanizing machine, and then carrying out secondary vulcanization in an oven under the vulcanization conditions of 175-DEG C, 4h, 195 ℃, 3h, 215 ℃ and 2h to obtain the graphene antistatic medical sole composite material.

Example 2

The embodiment provides a graphene antistatic medical sole composite material, which comprises the following raw materials in parts by weight: 28 parts of butyl rubber, 38 parts of natural rubber, 8 parts of butadiene rubber, 12 parts of ethylene propylene diene monomer, 4 parts of white carbon black, 3 parts of graphene, 5 parts of antistatic powder, 0.8 part of a flow aid, 6 parts of zinc oxide, 2 parts of zinc stearate, 0.8 part of stearic acid, 1.0 part of an odorless cross-linking agent and 3 parts of a foaming agent.

The embodiment also provides a preparation method of the graphene antistatic medical sole composite material, which comprises the following steps:

step 1, mixing a flow aid, stearic acid and deionized water according to a weight ratio of 0.8:0.8:100, heating to 120 ℃ after uniformly mixing, slowly and gradually adding graphene, stirring continuously, stirring for 3 hours after adding, wherein the adding amount of the graphene is 3mg/ml, obtaining the flow aid and the stearic acid-treated graphene, then sequentially adding butyl rubber, natural rubber, butadiene rubber and ethylene propylene diene monomer into the flow aid and the stearic acid-treated graphene, and mixing in a mixing mill at the mixing temperature of 140 ℃ for 5 hours to obtain mixed virgin rubber;

and 2, adding white carbon black, antistatic powder, zinc oxide, zinc stearate, an odorless cross-linking agent and a foaming agent into the mixed virgin rubber, carrying out hot pressing on the mixed virgin rubber for 28min at the temperature of 130 ℃ and under the pressure of 8Mpa on a flat vulcanizing machine, and then carrying out secondary vulcanization in an oven under the vulcanization conditions of 178 ℃, 4 hours, 200 ℃, 3 hours, 220 ℃ and 2 hours to obtain the graphene antistatic medical sole composite material.

Example 3

The embodiment provides a graphene antistatic medical sole composite material, which comprises the following raw materials in parts by weight: 30 parts of butyl rubber, 40 parts of natural rubber, 10 parts of butadiene rubber, 15 parts of ethylene propylene diene monomer, 5 parts of white carbon black, 5 parts of graphene, 5 parts of antistatic powder, 1.0 part of flow aid, 7 parts of zinc oxide, 2 parts of zinc stearate, 1 part of stearic acid, 1.5 parts of odorless cross-linking agent and 3 parts of foaming agent.

The embodiment also provides a preparation method of the graphene antistatic medical sole composite material, which comprises the following steps:

step 1, proportioning a flow aid, stearic acid and deionized water according to a weight ratio of 1.0:1.0:100, uniformly mixing, heating to 140 ℃, slowly and gradually adding graphene, stirring continuously, stirring for 2 hours continuously after adding, wherein the adding amount of the graphene is 5mg/ml, so as to obtain the flow aid and the stearic acid-treated graphene, then sequentially adding butyl rubber, natural rubber, butadiene rubber and ethylene propylene diene monomer into the flow aid and the stearic acid-treated graphene, and mixing in a mixing mill at the mixing temperature of 150 ℃ for 5 hours, so as to obtain mixed virgin rubber;

and 2, adding white carbon black, antistatic powder, zinc oxide, zinc stearate, an odorless cross-linking agent and a foaming agent into the mixed virgin rubber, carrying out hot pressing on the mixed virgin rubber for 25min at 140 ℃ and 10Mpa in a flat vulcanizing machine, and then carrying out secondary vulcanization in an oven under the vulcanization conditions of 180 ℃, 3 hours, 200 ℃, 2.5 hours, 220 ℃ and 1.5 hours to obtain the graphene antistatic medical sole composite material.

Example 4

The embodiment provides a graphene antistatic medical sole composite material, which comprises the following raw materials in parts by weight: 33 parts of butyl rubber, 33 parts of natural rubber, 13 parts of butadiene rubber, 18 parts of ethylene propylene diene monomer, 6 parts of white carbon black, 6 parts of graphene, 6 parts of antistatic powder, 1.2 parts of a flow aid, 8 parts of zinc oxide, 2 parts of zinc stearate, 1.5 parts of stearic acid, 2.0 parts of an odorless cross-linking agent and 4 parts of a foaming agent.

The embodiment also provides a preparation method of the graphene antistatic medical sole composite material, which comprises the following steps:

step 1, mixing a flow aid, stearic acid and deionized water according to a weight ratio of 1.2:1.5:100, heating to 150 ℃ after uniformly mixing, slowly and gradually adding graphene, stirring continuously, stirring for 2 hours after adding, wherein the adding amount of the graphene is 6mg/ml, so as to obtain the flow aid and the stearic acid-treated graphene, then sequentially adding butyl rubber, natural rubber, butadiene rubber and ethylene propylene diene monomer into the flow aid and the stearic acid-treated graphene, and mixing in a mixer at the mixing temperature of 170 ℃ for 4 hours, so as to obtain mixed virgin rubber;

and 2, adding white carbon black, antistatic powder, zinc oxide, zinc stearate, an odorless cross-linking agent and a foaming agent into the mixed virgin rubber, carrying out hot pressing on the mixed virgin rubber for 20min at the temperature of 150 ℃ and the pressure of 10Mpa on a flat vulcanizing machine, and then carrying out secondary vulcanization in an oven under the vulcanization conditions of 183 ℃, 3 hours, 200 ℃, 2 hours, 220 ℃ and 1.5 hours to obtain the graphene antistatic medical sole composite material.

Example 5

The embodiment provides a graphene antistatic medical sole composite material, which comprises the following raw materials in parts by weight: 35 parts of butyl rubber, 45 parts of natural rubber, 15 parts of butadiene rubber, 20 parts of ethylene propylene diene monomer, 8 parts of white carbon black, 10 parts of graphene, 8 parts of antistatic powder, 1.5 parts of a flow aid, 10 parts of zinc oxide, 3 parts of zinc stearate, 2 parts of stearic acid, 2.5 parts of an odorless cross-linking agent and 5 parts of a foaming agent.

The embodiment also provides a preparation method of the graphene antistatic medical sole composite material, which comprises the following steps:

step 1, mixing a flow aid, stearic acid and deionized water according to a weight ratio of 1.5:2:100, heating to 160 ℃ after uniformly mixing, slowly and gradually adding graphene, stirring continuously, stirring for 1h after adding, wherein the adding amount of the graphene is 10mg/ml, so as to obtain the flow aid and the stearic acid-treated graphene, then sequentially adding butyl rubber, natural rubber, butadiene rubber and ethylene propylene diene monomer into the flow aid and the stearic acid-treated graphene, and mixing in a mixing mill at 180 ℃ for 3h, so as to obtain mixed virgin rubber;

and 2, adding white carbon black, antistatic powder, zinc oxide, zinc stearate, an odorless cross-linking agent and a foaming agent into the mixed virgin rubber, carrying out hot pressing on the mixed virgin rubber for 20min at 160 ℃ and 10Mpa in a flat vulcanizing machine, and then carrying out secondary vulcanization in an oven under the vulcanization conditions of 185 ℃, 2h, 205 ℃, 2h, 225 ℃ and 1h to obtain the graphene antistatic medical sole composite material.

The mechanical property of the graphene antistatic medical sole composite material prepared in the above examples 1 to 5 can be tested, and the test method is as follows:

(1) and (4) detecting the volume resistivity and the surface conductivity according to a GB/T1410-2006 solid insulating material volume resistivity and surface resistivity test method.

(2) Tear strength: according to GB 6039-85, the tear strength is defined as: stretching the sample in the direction parallel to the main shaft of the sample until the maximum force is generated during cracking, preparing the sample according to the methods of GB529 and GB530, and standing the vulcanized test piece (the thickness is 2.0 +/-0.3 mm) in the testing step (1) at the standard room temperature (not less than 6 hours and not more than 15 days); (2) when a sample is taken, the direction of the bisector of the tearing angle of the cutter is consistent with the rolling direction; (3) vertically clamping the sample on an upper clamp and a lower clamp, and fully and uniformly clamping the sample at equal positions; (4) the tester is started after the stretching speed is adjusted (the tester is operated in a clamping device at the speed of 500 +/-100 mm/min), and then a gradually increased traction force can be applied to the test sample until the test sample is stopped after being torn off.

(3) Tensile strength: the procedure was followed according to ASTM D-412.

(4) Modulus: the method is carried out according to HG/T3321-2012 standard.

The test results were as follows:

TABLE 1 test results

Test results	Example 1	Example 2	Example 3	Example 4	Example 5
						Volume resistivity Ω · m	1015	1015	1015	1015	1015
Surface resistivity omega	1015	1015	1015	1015	1015
						Tear Strength kN/m	98	110	118	113	108
Tensile strength Mpa	33	34	38	37	35
						Modulus Mpa	2.7	3.1	3.3	3.0	2.8

Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.